JP2007527309A - Energy recovery method in aromatic carboxylic acid production process - Google Patents

Abstract

In the present invention, a method for producing an aromatic carboxylic acid by exothermic liquid phase oxidation of an aromatic feedstock is provided. More specifically, the present invention provides an efficient energy recovery method for the amount of heat generated by liquid phase oxidation of an aromatic feedstock. An apparatus that effectively recovers energy from the production of aromatic carboxylic acid by exothermic liquid phase oxidation of an aromatic feedstock is performed by the main energy recovery means increasing intermediate pressure steam. This is usually combined with a process known as the inherent Rankine cycle and / or a method of recovering low temperature energy using a heat pump. When these energy recovery methods are combined, energy recovery as a whole increases, and reaction energy can be recovered as either heat recovery (steam) or work, or a combination of both.
[Selection] Figure 1

Description

  The present invention relates to a process for producing concentrated aromatic carboxylic acid streams by exothermic liquid phase oxidation of aromatic feedstocks. More particularly, the present invention relates to efficient energy recovery of the calorific value generated by liquid phase oxidation of aromatic feedstocks.

  Aromatic carboxylic acids such as terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid are valuable compounds and raw materials for the production of polyesters. In the case of terephthalic acid, a single manufacturing facility can produce over 100,000 metric tons per year as a feedstock for polyethylene terephthalate (PET) facilities.

  Terephthalic acid (TPA) can be produced by high pressure, exothermic oxidation of a suitable aromatic feedstock such as paraxylene. Typically, these oxidations are performed in the liquid phase using air or an alternative source of molecular oxygen in the presence of a metal catalyst or promoter compound. Methods for oxidizing paraxylene and other aromatic compounds such as m-xylene and dimethylnaphthalene are well known in the art. These oxidation reactions typically produce a reaction gas that generally includes oxidation reaction products such as carbon monoxide, carbon dioxide, and methyl bromide. Further, when air is used as an oxygen source, the reaction gas includes nitrogen and excess oxygen.

  Further, most of the methods for producing TPA also use a low molecular weight carboxylic acid such as acetic acid as a part of the reaction solvent. Furthermore, some water is also present in the oxidation solvent, produced as an oxidation byproduct as well.

  This type of oxidation is generally highly exothermic and there are many ways to control these reaction temperatures, but a common and convenient method is to evaporate some of the solvent during the reaction. Is to remove the heat. The combination of reactive gas and volatile solvent is said to be a gas mixture. This gas mixture contains a considerable amount of energy.

  Since water is produced as an oxidation byproduct, at least a portion of the gas mixture is usually sent to a separator, typically a distillation column, either as a vapor or a condensate, and the water in the reactor. Water is separated from the primary solvent (eg, acetic acid) so that the concentrate does not accumulate.

  The object of the present invention is to provide an efficient and economical energy recovery method that recovers the energy generated as a result of a highly exothermic oxidation reaction that produces aromatic carboxylic acids. In another object of the present invention, an energy recovery method is provided in which energy is recovered simultaneously while chemically separating a low molecular weight carboxylic acid solvent and water.

According to a first embodiment of the present invention, the following steps:
a) oxidizing the aromatic feedstock with the liquid phase reaction mixture in the reaction zone to produce a concentrated aromatic carboxylic acid stream and gas mixture;
b) removing a substantial part of the solvent from the gas mixture in the separation zone to form an exhaust gas stream and a solvent-rich stream; and c) condensing the exhaust gas stream by condensing a part of the exhaust gas stream in the heat recovery zone. The condensed mixture is selectively returned to the separation zone, a portion of its thermal energy is recovered in the working fluid, and a portion of the enthalpy of the working fluid is recovered in the power cycle, thereby at least one of the exhaust gas streams. Recovering thermal energy from the part, wherein the working fluid is a compound having a normal boiling point of about −100 ° C. to about 90 ° C. or a mixture of such compounds;
A method for recovering thermal energy from an exhaust gas stream is provided.

According to another embodiment of the present invention, the following steps:
a) removing a substantial part of the oxidizing solvent from the gas mixture in the separation zone to form an exhaust gas stream; and b) optionally from a part of the exhaust gas stream in the first heat recovery device. Recovering thermal energy to produce low pressure steam;
c) recovering thermal energy from a portion of the exhaust gas stream using working fluid passing through the power cycle in the second heat recovery device, where a portion of the enthalpy in the working fluid is recovered in the power cycle. And the working fluid is a compound having a normal boiling point of about −100 ° C. to about 90 ° C. or a mixture of the compounds, and d) optionally in a third heat recovery device, Recovering thermal energy from a part,
A method for recovering thermal energy from an exhaust gas stream is provided.

According to yet another embodiment of the invention, the following steps:
a) oxidizing the aromatic feedstock with the liquid phase reaction mixture within the reaction zone to produce an aromatic carboxylic acid stream and a gas mixture;
b) removing a substantial part of the solvent from the gas mixture in the separation zone to form an exhaust gas stream; and c) optionally, heat energy from a part of the exhaust gas stream in the first heat recovery device. Recovering and generating low-pressure steam,
d) recovering thermal energy from a portion of the exhaust gas stream using a working fluid passing through the power cycle in a second heat recovery device, wherein the working fluid is about −100 ° C. to about 90 ° C. A compound having a normal boiling point or a mixture of such compounds; and e) optionally recovering thermal energy from a portion of the exhaust gas stream in a third heat recovery device;
A method for recovering thermal energy from an exhaust gas stream is provided.

According to yet another embodiment of the invention, the following steps:
a) oxidizing the aromatic feedstock with the liquid phase reaction mixture within the reaction zone to produce an aromatic carboxylic acid stream and a gas mixture;
b) removing a substantial part of the solvent from the gas mixture in the separation zone to form an exhaust gas stream;
c) recovering thermal energy from a portion of the exhaust gas stream in the first heat recovery device to generate low pressure steam;
d) recovering thermal energy from a portion of the exhaust gas stream using a working fluid passing through the power cycle in a second heat recovery device, wherein the working fluid is about −100 ° C. to about 90 ° C. A compound having a normal boiling point or a mixture of such compounds; and e) recovering thermal energy from a portion of the exhaust gas stream in a third heat recovery device;
Are provided in this order, and a method for recovering thermal energy from an exhaust gas stream is provided.

  In a first embodiment of the present invention, a method for recovering energy from the exhaust gas stream 145 is shown in FIG. This method includes the following steps.

  Stage (a) includes oxidizing the aromatic feed 105 with the liquid phase reaction mixture 110 in the reaction zone 115 to produce a concentrated aromatic carboxylic acid stream 120 and a gas mixture 125.

  The liquid phase reaction mixture 110 includes water, a solvent, a metal oxidation catalyst, and a molecular oxygen source. The reaction zone 115 includes at least one oxidation reactor. This oxidation is complete under reaction conditions that produce a concentrated aromatic carboxylic acid stream 120 and a gas mixture 125. Typically, the aromatic carboxylic acid rich stream 120 is a slurry of crude terephthalic acid.

  Crude terephthalic acid is usually produced via liquid-phase air oxidation of para-xylene in the presence of a heavy metal oxidation catalyst. Suitable catalysts include, but are not limited to, cobalt, manganese and bromide compounds that are soluble in the selected catalyst. Suitable solvents include, but are not limited to, aliphatic monocarboxylic acids having 2 to 6 carbon atoms, or benzoic acid and mixtures thereof and mixtures of these compounds with water. The solvent is preferably a mixture of acetic acid and water in a ratio of about 5: 1 to about 25: 1, preferably about 10: 1 to about 15: 1. However, it should be understood that other suitable solvents may be used, such as those described herein. Conduit 125 includes a gas mixture containing volatile solvents, gas by-products, nitrogen and unreacted nitrogen resulting from the exothermic liquid phase oxidation reaction from the aromatic feed to the aromatic carboxylic acid. Patents disclosing the production of terephthalic acid, such as US Pat. Nos. 4,158,738 and 3,996,271, are hereby incorporated by reference.

  Step (b) includes removing a substantial portion of the solvent from the gas mixture 125 within the separation zone 130 to form an exhaust gas stream 135 and a solvent rich stream 140.

  The exhaust gas stream 135 includes water, gas by-products, and a small amount of solvent. When the solvent is a low molecular weight carboxylic acid solvent, the ratio of water to low molecular weight carboxylic acid solvent ranges from about 80:20 to about 99.99: 0.01 by weight. Such gas by-products include oxygen, oxygen by-products such as carbon monoxide and carbon dioxide, and nitrogen when air is used as molecular oxygen. At least a portion of exhaust gas stream 135 or all of exhaust gas stream 135 is sent via conduit 145 to the heat recovery zone.

  Typically, the temperature and pressure conditions of the exhaust gas stream 145 range from about 130 to about 220 ° C. and from about 3.5 to about 18 bar. Preferably, the temperature and pressure conditions of the exhaust gas stream 145 range from about 90 to about 200 ° C. and from about 4 to about 15 bar. Most preferably, the temperature and pressure conditions of the exhaust gas stream 145 range from about 130 to about 180 ° C. and from about 4 to about 10 bar.

  The gas mixture in conduit 125 is directed to separation zone 130. Typically, the separation zone 130 includes a high pressure distillation column having about 20 to about 50 theoretical plates and a single condenser or multiple condensers. In the separation zone 130, a solvent rich stream is recovered via conduit 140. What is the purpose of the separation zone 130? Therefore, separation is performed in which at least part of the solvent is recovered and excess water is removed. In general, for optimum energy recovery purposes, the pressure reduction between the contents of conduit 125 and conduits 135 and 145 should indicate a potential recovery energy loss, so that pressure reduction should be minimized. . Thus, the separation zone 130 must be operated at temperature and pressure conditions that are the same as or close to that of the gas mixture from conduit 125. At least a portion or all of the exhaust gas stream 135 is sent via conduit 145 to the heat recovery zone, and the remainder 137 of the exhaust gas stream is utilized anywhere in the aromatic carboxylic acid production process.

  Step (c) includes recovering thermal energy from at least a portion of the exhaust gas stream 145 within the heat recovery zone 150. In the heat recovery zone 150, a portion of the exhaust gas stream 145 is condensed to produce a condensed mixture 155 that is selectively returned to the separation zone. A working fluid is used to recover the thermal energy. Generally, the working fluid is a compound or mixture of compounds having a normal boiling point of about −100 ° C. to about 90 ° C.

  Recovery of thermal energy from the exhaust gas stream 145 within the heat recovery zone 150 may be performed by any means known in the art. In general, however, a power cycle is used. Power cycles are well known in the art. A power cycle is a cycle that takes heat and uses it to work on the surroundings. There are many power cycles well known in the art. Specific examples of a power cycle include a power cycle as described in an intrinsic Rankine cycle (ORC), a carina cycle, or WO 02/063141, which is incorporated herein by reference. However, it is not limited to these.

  Other specific examples of power cycles that can be used are: Energy, Vol. 22, No. 7, 661-667, 1997, Elsevier Science, UK, “A Review of Organic Rankine Cycles (ORC) for the “Recovery of Low-Grade Waste Heat”, and Energy, Vol. 21, No. 1, pp. 21-27, 1996, Elsevier Science In the UK, under the heading “Absorption Power Cycles” (which is incorporated herein by reference).

  One common feature between these embodiments is the use of a low temperature evaporation working fluid. Typically, a low temperature evaporation working fluid is a power cycle for recovering thermal energy at relatively low temperatures (eg, generally below 150 ° C.) instead of water or steam for high power recovery efficiency. Is used. One such cycle characterized by an isothermal boiling / condensation process is the Rankine cycle. Steam turbine plants are usually very close to the Rankine cycle process where the working fluid is substantially water. However, although usually accepted, Rankine cycle power recovery using water / steam at low temperatures (eg, generally below 150 ° C.) is generally inefficient.

  The working fluid may be any fluid as long as it is substantially free of water (substantially free of water is approximately less than 20% by weight). In another embodiment of the invention, the working fluid is a compound or mixture of compounds having a normal boiling point of about −100 ° C. to about 90 ° C. In other ranges, the working fluid may be a compound having a normal boiling point of about −100 ° C. to about 60 ° C. or a mixture of such compounds.

  In another embodiment of the invention, the working fluid is selected from the group consisting of propane, isopropane, isobutane, butane, isopentane, n-pentane, ammonia, R134a, R11, R12, and mixtures thereof. R134a, R11, and R12 are refrigerants that are known in the art and are commercially available.

  In a second embodiment of the present invention, a method for recovering thermal energy from at least a portion of exhaust gas stream 235 via conduit 245 is shown in FIG. The method includes the following steps.

  Stage (a) includes removing a substantial portion of the solvent from the gas mixture 225 in the separation zone 230 to form an exhaust gas stream 235 and a solvent rich stream 240.

  Step (a) in the second embodiment is substantially the same as step (b) in the first embodiment of the present invention. If the separation zone includes a distillation column, the exhaust gas stream 245 exits the top of the distillation column through conduits 245 and 237. The exhaust gas stream 245 includes gas reaction byproducts, nitrogen, and unreacted oxygen. The solvent, typically acetic acid and water, is also present in or near saturation conditions. The ratio of water to acetic acid is roughly in the range of 80:20 to 99.99: 0.01, preferably in the range of 99.5: 0.5 to 98.5: 1.5 by mass. is there. A portion of this exhaust gas stream, represented by the contents of conduit 245, may pass through a series of heat recovery zones 260, 270, and 280. A portion of the exhaust gas stream 245 is condensed and travels as a reflux via conduit 255 to the distillation tower of separation zone 230 or as a liquid agglomerate via conduit 285.

  From a distillation standpoint, the heat recovery zones 260, 270, and 280 are responsible for fully condensing the material from the exhaust gas stream 245 on the tower and allowing solvent and water to flow to the distillation tower in the separation zone 230. To provide a suitable reflux for separation. However, the thermal efficiency required to perform the condensation also helps to remove the heat generated by the oxidation reaction from the aromatic feed to the aromatic carboxylic acid.

  Recovering energy is generally effective and efficient. One obstacle to efficient energy recovery is the presence of noncondensable gases in conduits 245 and 237. This non-condensable gas, such as nitrogen, oxygen, carbon monoxide, and carbon dioxide, produces a condensation heat curve that makes vapor generation difficult.

  This is illustrated by the specific example of FIG. FIG. 3 shows a “condensation curve” that describes the thermal efficiency of the condenser or partial condenser as a function of temperature. In this case, the condenser is a condenser with a steam inlet temperature of about 139 ° C and an outlet temperature of about 45 ° C.

  If it is desired to generate about 15 psig (ie, 1 bar) of steam in a single condensing unit, then in FIG. 3, using only 55% of the total efficiency of the condenser, 15 psig It is shown that it is sufficient to generate the steam. This is because 15 psig steam has a saturation temperature of about 121 ° C. In this partial condenser example, it is possible to convert to steam at a temperature of 121 ° C. or above with a thermal efficiency of only 55% of the total efficiency. This explains what is normally known in the heat exchange technology as a temperature “insufficient” and indicates the thermodynamic limit of the system.

  If the pressure (and temperature) of the generated steam is low, more heat can be recovered. However, this is a critical value because the steam must be at a sufficient temperature in order to utilize it for heating purposes elsewhere in the carboxylic acid production process.

  Step (b) optionally includes recovering thermal energy from a portion of the exhaust gas stream 245 to produce low pressure steam within the first heat recovery zone 260.

  In step (c), in the second heat recovery zone 270, the working fluid passing through the power cycle is used to recover thermal energy from a portion of the exhaust gas stream 245, where the working fluid is about − A compound having a normal boiling point of 100 ° C. to about 90 ° C. or a mixture of such compounds.

  Step (d) includes recovering thermal energy from a portion of the exhaust gas stream 245 within the third heat recovery zone 280.

  The purpose of step (b), step (c) and step (d) is the efficient recovery of thermal energy. The heat recovery zones 260, 270 and 280 include at least one device for recovering thermal energy from the exhaust gas stream 145. The first heat recovery zone 260 includes a single heat recovery device or a plurality of heat recovery devices where heat exchange is achieved at temperatures above about 121 ° C. The second heat recovery zone 270 includes a single heat recovery device or a plurality of heat recovery devices in which heat exchange is achieved at a temperature greater than 90 ° C. The third heat recovery zone 280 includes a single heat recovery device or a plurality of heat recovery devices where heat exchange is achieved at temperatures above 25 ° C. The heat recovery device may be any device known in the art.

  The relevance of the heat recovery temperatures is evident in the efficiency and effectiveness of the heat recovered at those temperatures. At temperatures above 121 ° C., the heating medium can generate about 15 psig (about 1 bar) of saturated steam that is useful for industrial applications such as the production of aromatic carboxylic acids. Although it is possible to generate larger quantities of steam at lower temperatures, the usefulness of such steam is limited. Furthermore, the use of steam as a heat transfer medium for heat exchange to a cryogenic fluid is very effective thermodynamically.

  The first heat recovery zone 260 typically includes, but is not limited to, a condenser.

  The second heat recovery zone 270 typically includes a heat exchange device, such as a condenser or partial condenser, that transfers heat to a “working fluid”, usually a refrigerant compound or a hydrocarbon or hydrocarbon mixture. Is included, but is not limited thereto. In the case of heat and energy recovery at temperatures close to or above 90 ° C., several methods are known in the art.

  The working fluid may be any fluid as long as it is substantially free of water (substantially containing less than about 20% water by weight). In another embodiment of the invention, the working fluid is a compound or mixture of compounds having a normal boiling point of about −100 ° C. to about 90 ° C. In other ranges, the fluid may be a compound having a normal boiling point of about −100 ° C. to about 60 ° C. or a mixture of such compounds.

  In another embodiment of the invention, the working fluid is selected from the group consisting of propane, isopropane, isobutane, butane, isopentane, n-pentane, ammonia, R134a, R11, R12, and mixtures thereof. R134a, R11, and R12 are known in the art and are usually commercially available as refrigerants.

  Specific examples of power cycles include, but are not limited to, inherent Rankine cycles, carina cycles, or power cycles as described in WO 02/063141.

  The inherent Rankine cycle (ORC) has been known to effectively and economically recover mechanical work and / or electricity from industrial waste heat. In practice, due to the irreversibility of thermodynamic systems, it is impossible to convert all of the available thermal energy into useful work. However, because the usefulness of low pressure steam is limited, it is much more economically advantageous to recover energy by some other means besides generated steam.

  There are several examples of industrial methods that utilize an ORC system for energy recovery. The main advantage of the OCR is its excellent ability to recover low to medium temperature waste heat. In the case of an ORC system that recovers energy in the range of 90 ° C. to 120 ° C., the system has an efficiency of 3-20%. System efficiency is defined as the total work derived from the ORC system divided by the total incoming waste heat. The main factors that determine system efficiency are the work temperature associated with the waste heat stream, the condenser temperature and the thermodynamic properties of the working fluid.

  Alternatively, the second heat recovery zone 270 serves to transfer heat to the heat pump system. A number of heat pump systems are known in the art. Thus, any system that can efficiently recover energy from low temperature heat is available.

  The third heat recovery zone 280 includes a single heat recovery device or a plurality of heat recovery devices where heat exchange is achieved at or near temperatures above 25 ° C. Typically, the third heat recovery zone 280 includes a water cooled or air cooled condenser or partial condenser.

  In a third embodiment of the present invention, a method for recovering thermal energy from the exhaust gas stream 235 is shown in FIG. The method includes the following steps.

  Stage (a) includes oxidizing aromatic feed 205 with liquid phase reaction mixture 210 within reaction zone 215 to produce aromatic carboxylic acid rich stream 220 and gas mixture 225.

  Step (a) in the third embodiment of the present invention is the same as step (a) in the first embodiment.

  Step (b) includes removing a substantial portion of the solvent from the gas mixture 225 within the separation zone 230 to provide an exhaust gas stream 235 and a solvent rich stream 240.

  Step (b) in the third embodiment is substantially the same as step (b) in the first embodiment of the present invention.

  Step (c) optionally includes recovering thermal energy from a portion of the exhaust gas stream 245 within the first heat recovery zone 260 to produce low pressure steam.

  In step (d), in the second heat recovery zone 270, the working fluid in the power cycle (where the working fluid is a compound having a normal boiling point of about −100 ° C. to about 90 ° C. or a mixture of such compounds). Recovering thermal energy from a portion of the exhaust gas stream 245.

  Step (e) includes recovering thermal energy from at least a portion of the exhaust gas stream 245 within the third heat recovery zone 280.

  Step (c), step (d) and step (e) in the third embodiment of the present invention are the same as step (b), step (c) and step (d) in the second embodiment of the present invention, respectively. Is substantially the same.

  The invention is further illustrated by the following examples which are preferred embodiments thereof, which examples are included solely for the purpose of illustrating the invention and, unless otherwise indicated, the technology of the invention. It will be understood that the scope is not limited.

  FIG. 4 shows an embodiment of the power recovery system. Temperature and pressure are consistent with the production of terephthalic acid. In this system, the working fluid for the inherent Rankine cycle system is n-pentane. The results based on ASPEN Plus® computer simulation are shown in Table 2. Details of the equipment used in the model are shown in Table 1. In this example, 15 psig of steam is generated using a total thermal efficiency of about 55%. For an additional 38% total thermal efficiency, an ORC system that enhances energy recovery is used. The overall thermal efficiency of the ORC system is roughly about 7.3%. Assume that significant improvements are made by optimizing working fluid selection and optimizing ORC system temperature and pressure conditions.

1 illustrates one embodiment of the present invention for recovering thermal energy from an exhaust gas stream. Fig. 4 illustrates another embodiment of the present invention for recovering thermal energy from an exhaust gas stream. 2 shows a “condensation curve” describing the thermal efficiency as a function of temperature in the condenser or partial condenser in the present invention. 1 shows a specific example of a power recovery system according to the present invention.

Explanation of symbols

105 Aromatic Feedstock 110 Liquid Phase Reaction Mixture 115 Reaction Zone 120 Aromatic Carboxylic Acid Concentrated Flow 125 Gas Mixture 130 Separation Zone 135 Exhaust Gas Stream 137 Remaining Exhaust Gas Stream 140 Solvent Concentrated Stream 145 Part of Exhaust Gas Stream 150 Heat Recovery Zone 155 Condensation Mixture 205 Aromatic feed 210 Liquid phase reaction mixture 215 Reaction zone 220 Aromatic carboxylic acid rich stream 225 Gas mixture 230 Separation zone 235 Exhaust gas stream 237 Remaining exhaust gas stream 240 Solvent rich stream 245 Part of exhaust gas stream 255 To separation zone Conduit 260 First heat recovery zone 270 Second heat recovery zone 280 Third heat recovery zone 285 Liquid distillate conduit 321 Steam generator 322 Evaporator 500 Turbine 510 Condenser 520 Pump

Claims (34)

The following stages,
a) oxidizing the aromatic feedstock with the liquid phase reaction mixture in the reaction zone to produce a concentrated aromatic carboxylic acid stream and gas mixture;
b) removing a substantial part of the solvent from the gas mixture in the separation zone to form an exhaust gas stream and a solvent rich stream; and c) condensing a part of the exhaust gas stream in the heat recovery zone. A condensate mixture, selectively returning the condensate mixture to the separation zone, recovering its thermal energy to the working fluid, and recovering a portion of the enthalpy of the working fluid to the power cycle, thereby at least one of the exhaust gas streams. Recovering thermal energy from the part, wherein the working fluid is a compound having a normal boiling point of about −100 ° C. to about 90 ° C. or a mixture of such compounds,
A method for recovering thermal energy from an exhaust gas stream.   The method of claim 1, wherein a portion of thermal energy from the exhaust gas stream is used to generate steam.   The method of claim 1, wherein the working fluid is selected from the group consisting of propane, isopropane, isobutane, butane, isopentane, n-pentane, ammonia, R134a, R11, R12, and mixtures thereof.   The method of claim 2, wherein the working fluid is selected from the group consisting of propane, isopropane, isobutane, butane, isopentane, n-pentane, ammonia, R134a, R11, R12, and mixtures thereof.   The method of claim 4, wherein the separation zone comprises a distillation column.   6. The method of claim 5, wherein the distillation column is operated at a temperature of about 130 <0> C to about 220 <0> C.   The process according to claim 6, wherein the distillation column is operated under a pressure of about 3.5 bar to about 15 bar.   The method of claim 1, wherein the power cycle is an intrinsic Rankine cycle or a carina cycle. The following stages,
a) removing a substantial portion of the solvent from the gas mixture in the separation zone to form an exhaust gas stream and a solvent rich stream; and b) optionally, in the first heat recovery zone, the exhaust gas stream. Recovering thermal energy from a part to produce low-pressure steam,
c) recovering thermal energy from a portion of the exhaust gas stream using a working fluid within a second heat recovery zone, wherein a portion of the enthalpy in the working fluid is recovered in a power cycle; The working fluid is a compound having a normal boiling point of about −100 ° C. to about 90 ° C. or a mixture of such compounds; and d) optionally from a portion of the exhaust gas stream in a third heat recovery zone. Recovering thermal energy,
A method for recovering thermal energy from an exhaust gas stream.   The method of claim 9, wherein the power cycle is an intrinsic Rankine cycle or a carina cycle.   10. The method of claim 9, wherein the working fluid is selected from the group consisting of propane, isopropane, isobutane, butane, isopentane, n-pentane, ammonia, R134a, R11, R12, and mixtures thereof.   The method of claim 9, wherein the working fluid is a compound or mixture of compounds having a normal boiling point of about −100 ° C. to about 60 ° C.   The method of claim 1, wherein the first heat recovery zone comprises a heat recovery device operated at a temperature of about −100 ° C. to about 60 ° C.   The method of claim 13, wherein the second heat recovery zone comprises a heat recovery device operated at a temperature of about 80 ° C. to about 120 ° C.   The method of claim 14, wherein the third heat recovery zone comprises a heat recovery device operated at a temperature of about 20 ° C. to about 120 ° C.   The method of claim 15, wherein the first heat recovery zone includes a partial condenser.   The method of claim 16, wherein the second heat recovery zone comprises a heat recovery device selected from the group consisting of a condenser and a partial condenser.   The method of claim 17, wherein the third heat recovery zone comprises a heat recovery device selected from the group consisting of a water cooling device and an air cooling device. The following stages,
a) oxidizing the aromatic feedstock with the liquid phase reaction mixture within the reaction zone to produce an aromatic carboxylic acid stream and a gas mixture;
b) removing a substantial part of the solvent from the gas mixture in the separation zone to form an exhaust gas stream and a solvent rich stream; and c) optionally, in the first heat recovery zone, the exhaust gas stream. Recovering thermal energy from a part of the gas to produce low-pressure steam,
d) recovering thermal energy from a portion of the exhaust gas stream using a working fluid in a power cycle within a second heat recovery zone, wherein the working fluid is about −100 ° C. to about 90 ° C. A compound having a normal boiling point or a mixture of the compounds,
e) optionally recovering thermal energy from a portion of the exhaust gas stream in a third heat recovery zone;
For recovering thermal energy from an exhaust gas stream containing   The method of claim 19, wherein the first heat recovery zone comprises a heat recovery device operated at a temperature of about 100 ° C. to about 160 ° C.   21. The method of claim 20, wherein the second heat recovery zone comprises a heat recovery device operated at a temperature of about 80C to about 120C.   The method of claim 21, wherein the third heat recovery zone comprises a heat recovery device operated at a temperature of about 20 ° C. to about 100 ° C.   23. The method of claim 22, wherein the first heat recovery zone includes a condenser.   24. The method of claim 23, wherein the second heat recovery zone comprises a heat recovery device selected from the group consisting of a condenser and a partial condenser.   25. The method of claim 24, wherein the third heat recovery zone comprises a heat recovery device selected from the group consisting of a water cooling device and an air cooling device.   20. The method of claim 19, wherein the power cycle is an intrinsic Rankine cycle or a carina cycle. The following stages,
a) oxidizing the aromatic feedstock with the liquid phase reaction mixture within the reaction zone to produce an aromatic carboxylic acid stream and a gas mixture;
b) removing a substantial part of the solvent from the gas mixture in the separation zone to form an exhaust gas stream and a solvent-rich stream; and c) from a part of the exhaust gas stream in the first heat recovery zone. Recovering thermal energy to produce low pressure steam;
d) recovering thermal energy from a portion of the exhaust gas stream using a working fluid in a power cycle within a second heat recovery zone, wherein the working fluid is about −100 ° C. to about 90 ° C. E) recovering thermal energy from a portion of the exhaust gas stream in a third heat recovery zone, being a compound having a normal boiling point or a mixture of such compounds;
A method for recovering thermal energy from an exhaust gas stream.   28. The method of claim 27, wherein the first heat recovery zone includes a heat recovery device operated at a temperature of about 100 <0> C to about 160 <0> C.   30. The method of claim 28, wherein the second heat recovery zone comprises a heat recovery device operated at a temperature of about 80 <0> C to about 120 <0> C.   30. The method of claim 29, wherein the third heat recovery zone comprises a heat recovery device operated at a temperature of about 20 <0> C to about 100 <0> C.   32. The method of claim 30, wherein the first heat recovery zone includes a condenser.   32. The method of claim 31, wherein the second heat recovery zone comprises a heat recovery device selected from the group consisting of a condenser and a partial condenser.   33. The method of claim 32, wherein the third heat recovery zone comprises a heat recovery device selected from the group consisting of a water cooling device and an air cooling device.   28. The method of claim 27, wherein the power cycle is an intrinsic Rankine cycle or a carina cycle.

Images